2,3,4,6-tetra-O-benzyl-D-galactopyranose

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-benzyl-D-galactopyranose
• 英文别名: 2,3,4,6-tetra-O-benzyl-β-D-galactopyranose；(2R,3R,4S,5S,6R)-3,4,5-tris(benzyloxy)-6-[(benzyloxy)methyl]oxan-2-ol；(2R,3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-ol
• 化学式: C₃₄H₃₆O₆
• 分子量: 540.656
• InChiKey: OGOMAWHSXRDAKZ-BWNLSPMZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  40
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzyl-D-galactopyranose 在 三氟甲磺酸酐 、 氢气 、 sodium methylate 、 palladium(II) hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 生成 (2S,3S,4R)-2-azido-3,4-O-isopropylidene-1,3,4-octadecanetriol
  参考文献：
  名称：

  [EN] NKT CELL LIGANDS AND METHODS OF USE
  [FR] LIGANDS DE CELLULES NKT ET PROCÉDÉS D'UTILISATION

  摘要：

  本发明揭示了能够激活NKT细胞的α-糖苷鞘氨醇化合物及其组合物。本发明还揭示了激活NKT细胞的方法，刺激受试者的免疫反应的方法，以及使用这些化合物和组合物治疗癌症、传染病、自身免疫疾病和障碍，或过敏疾病或障碍的方法。

  公开号：

  WO2014210522A1
• 作为产物：
  描述：

  2-propynyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside 在 四氧化锇 、 N-甲基吲哚酮 、 potassium tert-butylate 、 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 16.0h， 生成 2,3,4,6-tetra-O-benzyl-D-galactopyranose
  参考文献：
  名称：

  Study of metal and acid catalysed deprotection of propargyl ethers of alcohols via their allenyl ethers

  摘要：

  A new method for the deprotection of prop-2-ynyl ethers 1b-9b is described. Isomerisation of 1b-9b to O-allenyl ethers 1d-9d and deprotection by reaction with Hg(OCOCF3)(2), aq.HCl, aq.CF3CO2H and best by use of a catalytic amount of OsO4 is described to obtain the alcohols 1a-9a in good yield. Application of this method for the deprotection of prop-2-enyl ethers 7c,8c,10c-13c via their corresponding prop-1-enyl ethers 7e,8e,10e-13e to obtain the corresponding alcohols 7a,8a,10a-13a is also described, (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(99)00631-6

文献信息

• Fluorine-Directed β-Galactosylation: Chemical Glycosylation Development by Molecular Editing
  作者：Estelle Durantie、Christoph Bucher、Ryan Gilmour

  DOI：10.1002/chem.201200468

  日期：2012.6.25

  Validation of the 2‐fluoro substituent as an inert steering group to control chemical glycosylation is presented. A molecular editing study has revealed that the exceptional levels of diastereocontrol in glycosylation processes by using 2‐fluoro‐3,4,6‐tri‐O‐benzyl glucopyranosyl trichloroacetimidate (TCA) scaffolds are a consequence of the 2R,3S,4S stereotriad. This study has also revealed that epimerization

  提出了将2-氟取代基作为控制化学糖基化反应的惰性指导基团的验证方法。一项分子编辑研究表明，通过使用2-氟-3,4,6-三-O-苄基吡喃葡萄糖基三氯乙酰亚氨酸酯（TCA）支架，糖基化过程中非对映异构控制的异常水平是2 R，3 S，4的结果S立体三合会。这项研究还表明，C4的差向异构作用会导致β选择性大大提高（高达β/α300：1）。
• Establishment of Guidelines for the Control of Glycosylation Reactions and Intermediates by Quantitative Assessment of Reactivity
  作者：Chun‐Wei Chang、Chia‐Hui Wu、Mei‐Huei Lin、Pin‐Hsuan Liao、Chun‐Chi Chang、Hsiao‐Han Chuang、Su‐Ching Lin、Sarah Lam、Ved Prakash Verma、Chao‐Ping Hsu、Cheng‐Chung Wang

  DOI：10.1002/anie.201906297

  日期：2019.11.18

  Stereocontrolled chemical glycosylation remains a major challenge despite vast efforts reported over many decades and so far still mainly relies on trial and error. Now it is shown that the relative reactivity value (RRV) of thioglycosides is an indicator for revealing stereoselectivities according to four types of acceptors. Mechanistic studies show that the reaction is dominated by two distinct intermediates:

  尽管数十年来进行了大量的努力，但立体控制的化学糖基化仍然是一个主要挑战，到目前为止，仍然主要依靠反复试验。现在表明，硫糖苷的相对反应性值（RRV）是根据四种受体揭示立体选择性的指标。机理研究表明，该反应由两种不同的中间体控制：糖基三氟甲磺酸酯和来自N-卤代琥珀酰亚胺（NXS）/ TfOH的糖基卤化物。糖基卤化物的形成与α-糖苷的产生高度相关。这些发现使得能够通过使用RRV作为α/β-选择性指示剂来预见糖基化反应，并且为立体控制糖基化开发了指导方针和规则。
• Carbohydrate-derived iminium salt organocatalysts for the asymmetric epoxidation of alkenes
  作者：Philip C. Bulman Page、Yohan Chan、John Liddle、Mark R.J. Elsegood

  DOI：10.1016/j.tet.2014.07.052

  日期：2014.10

  A new family of carbohydrate-based dihydroisoquinolinium salts has been prepared and tested for potential as asymmetric catalysts for the epoxidation of unfunctionalized alkene substrates, providing up to 57% ee in the product epoxides.

  已经制备了新的基于碳水化合物的二氢异喹啉鎓盐家族，并测试了其作为非对称催化剂用于未官能化烯烃底物环氧化的潜力，在产物环氧化物中提供高达57％ee。
• Synthesis of D-Galactopyranosylphosphonic and (D-Galactopyranosylmethyl)phosphonic Acids as Intermediates of Inhibitors of Galactosyltransferases
  作者：Helena Heissigerová、Petr Kočalka、Martina Hlaváčková、Anne Imberty、Christelle Breton、Valerie Chazalet、Jitka Moravcová

  DOI：10.1135/cccc20061659

  日期：——

  Employing the Michaelis-Arbuzov reaction of 1-O-acetyl-2,3,4,6-tetra-O-benzyl-D-galactopyranose with triethyl phosphite and trimethylsilyl trifluoromethanesulfonate, α- and β-D-galactopyranosylphosphonic acids were prepared in 33 and 28% yields, respectively. (α-D-Galactopyranosylmethyl)phosphonic acid was synthesized by a five-step route from 2,3,4,6-tetra-O-benzyl-D-galactopyranose in 52% overall yield. When tested against bovine α-1,3- and β-1,4-galactosyltransferases, all three compounds showed, at best, very poor inhibitions. Both enzymes were inhibited more effectively by β-D-galactopyranosylphosphonic acid (IC₅₀ = 17 mmol l^-1 at 13.5 μmol l^-1 of UDP-Gal for β4GalT).

  采用1-O-乙酰基-2,3,4,6-四-O-苄基-D-半乳糖吡喃糖与三乙基膦酸酯和三甲基硅基三氟甲磺酸酯的Michaelis-Arbuzov反应，分别以33%和28%的收率制备了α-和β-D-半乳糖吡喃糖基膦酸。(α-D-半乳糖吡喃糖基甲基)膦酸是通过从2,3,4,6-四-O-苄基-D-半乳糖吡喃糖出发的五步路线合成的，总收率为52%。在测试对牛α-1,3-和β-1,4-半乳糖基转移酶的抑制作用时，所有三种化合物显示出的抑制作用都很弱。两种酶都更有效地被β-D-半乳糖吡喃糖基膦酸抑制（IC₅₀ = 17 mmol l^-1，在13.5 μmol l^-1的UDP-半乳糖浓度下对β4GalT）。
• Enzyme-catalyzed synthesis of isosteric phosphono-analogues of sugar nucleotides
  作者：Stephen A. Beaton、Malcolm P. Huestis、Ali Sadeghi-Khomami、Neil R. Thomas、David L. Jakeman

  DOI：10.1039/b808078j

  日期：——

  Efficient enzymatic syntheses of isosteric phosphono analogues of sugar nucleotides have been accomplished using a thymidylyltransferase.

  利用胸苷酰基转移酶，已经成功实现了糖核苷酸等效磷酸类似物的酶促高效合成。